CN101928938A

CN101928938A - Manufacture method with polymer elements of plated film

Info

Publication number: CN101928938A
Application number: CN2010102041690A
Authority: CN
Inventors: 太田宽纪; 游佐敦; 阿野哲也
Original assignee: Hitachi Maxell Ltd
Current assignee: Maxell Holdings Ltd
Priority date: 2009-06-17
Filing date: 2010-06-12
Publication date: 2010-12-29
Also published as: EP2270256A3; EP2270256A2; US20100320635A1; JP2011001577A; KR20100135671A

Abstract

The invention provides a kind of manufacture method with polymer elements of plated film, utilize the carbon dioxide pressurized polymer elements that will be dispersed with catalyst component to carry out plated film under normal pressure and handle, acquisition has the polymer elements of the plated film of adaptation excellence.The present invention forms the polymer elements that is dispersed with catalyst component by the pressure fluid that utilizes the catalyst component that will contain the metal that becomes catalyzer to be dissolved in the carbonic acid gas gained, this polymer elements that is dispersed with catalyst component be impregnated in pure treatment solution under normal pressure, and then will under normal pressure, flood and the chemical plating liquid that contains alcohol, thereby form plated film by the pretreated polymer elements of pure treatment solution.

Description

Manufacture method with polymer elements of plated film

Technical field

The present invention relates to have the manufacture method of the polymer elements of the plated film that forms by chemical plating.

Background technology

In the past, as the method that forms metallic membrane on the surface of polymer elements, known had a chemical plating method.Because this chemical plating method is to utilize the chemical reaction reducing metal ion of catalyzer, on plated body, form the method for metallic membrane thus, except plated body self shows the situation of catalyst activity to the reductive action of reductive agent, must make metallics stable and adhere to equably in order to ensure the adaptation of the plating film of final gained in the interior surface of plated body with catalyst activity.Therefore, at plated body is under the situation of polymer elements such as resin molded body, before handling, use chemical plating the etching solution that contains the big oxygenant of carrying capacities of environment such as sexavalence chromic acid, permanganic acid that the alligatoring etch processes is carried out on the surface of polymer elements, form concavo-convexly on the surface of resin molded body, adhere to the metallics that becomes catalyst core at this concavo-convex place.In addition,, that is, can be fit to the polymer elements of chemical plating, be defined as and contain the polymer elements that ABS is a resin as by above-mentioned etching solution polymers impregnated parts.This be because, ABS is that resin contains can etched liquid selectivity erosive divinyl rubber composition, with respect to this, other resins can etched liquid selectivity erosive mentioned component seldom, the surface is difficult to form concavo-convex.Thus, be that the polymer elements of polycarbonate resin outside the resin etc. carries out chemical plating when handling to contain ABS as resinous principle, for make chemical plating become may and use that to contain ABS be resin or elastomeric plating level (め one I グレ one De) product.Yet in the above-mentioned plating level product, the reduction of the resistance toheat of main raw etc. is inevitable.

In order to address the above problem, the method of following formation polymer elements has been proposed, promptly before chemical plating is handled, utilize pressure fluids such as supercritical carbon dioxide, the catalyst components such as metal complex that will contain as the metal of plating catalyzer disperse.For example, contact with the pressure fluid that makes catalyst component be dissolved in supercritical co by the resin molded body that makes shaping, obtain being dispersed with the method for the polymer elements of catalyst component, or molten resin is contacted in cylinder with the pressure fluid that makes catalyst component be dissolved in supercritical co, and with this molten resin injection forming, thereby obtain being dispersed with the method (patent documentation 1) of the polymer elements of catalyst component.Supercutical fluid is to have concurrently as the impregnability of gas with as the fluid of the solvent properties of liquid, be dissolved with the pressure fluid of above-mentioned catalyst component by use, owing to be accompanied by soaking into of pressure fluid, be dissolved in this and flow intravital catalyst component and soak into to resin molded body or molten resin, therefore need not carry out etch processes can form the polymer elements that is dispersed with catalyst component.Therefore,, need not the big oxygenants such as sexavalence chromic acid of environment for use load according to aforesaid method, even and if for the few polymer elements of etched liquid erosive composition, also can handle and form plated film by chemical plating.

Yet, will by the resulting polymer elements of method that uses above-mentioned pressure fluid under the situation of carrying out the chemical plating processing under the normal pressure, have the low problem of closing force of formed plated film.Promptly, after existing etch processes, carry out in the method for chemical plating processing, to because etch processes is formed with the additional plating catalyzer of concavo-convex polymer elements on the surface, with the existing plating catalyzer in this concavo-convex inside as catalyst core and the growing metal particle.Therefore,, fill up concavo-convexly at the plated film at the interface of plated film and polymer elements, obtain the closing force of plated film thus in the inside of polymer elements.With respect to this, though pressure fluid is impregnated into polymer elements, but not polymer elements to be corroded as etch processes, and since pressure fluid be not only polymer elements surface but soak into to deep inside, at the plating catalyst concentration step-down of the near surface that can obtain high pinning effect.Particularly, as the employing injection molding method of patent documentation 1 catalyst component is scattered under the situation in the molten resin, owing to the proportion of the catalyst component that contains metal for the proportion of resinous principle is bigger, the plating catalyst concentration that the near surface of polymer elements exists reduces.Therefore, when using pressure fluid that catalyst component is scattered in polymer elements, amount for the plating catalyzer that increases the polymer elements near surface, be necessary to use the catalyst components such as metal complex that become the plating catalyzer with high as far as possible concentration dissolved pressure fluid, but during the chemical plating under normal pressure is handled, because chemical plating liquid is difficult to soak into the inside to polymer elements, even use high density ground to be dissolved with under the situation of pressure fluid of catalyst component, plated film also is that the plating catalyzer from the outmost surface that is present in polymer elements begins to grow.In view of the above,, can not form the plated film of the state of embedded resin in polymer elements inside, can not get high pinning effect even improve the plated film density of the outmost surface of polymer elements.

To this, the applicant etc. have proposed following method, promptly after using pressure fluid catalyst component is dissolved in carbon dioxide pressurized to be dispersed with the polymer elements of catalyst component with formation, further utilization contains carbon dioxide pressurized and pure chemical plating liquid this polymer elements is carried out the chemical plating processing, makes plated film begin growth (patent documentation 2) from the inside of polymer elements in view of the above.Though the chemical plating liquid that with water is main component is difficult to mix with carbon dioxide pressurized, by alcohol is mixed with chemical plating liquid, is not dissolved in the chemical plating liquid even do not stir the carbonic acid gas that also can make high pressure conditions.Therefore, impregnated in the above-mentioned chemical plating liquid by the polymer elements that high density is dispersed with catalyst component, film coating composition is with the carbon dioxide pressurized and pure inside that is impregnated into polymer elements, can be the catalyst core plated film of growing in view of the above with the plating catalyzer that is dispersed to polymer elements inside.

Patent documentation 1: specially permit communique No. 3696878

Patent documentation 2: specially permit communique No. 4092364

Summary of the invention

Yet, even under the situation of stating in the use that contains carbon dioxide pressurized and pure chemical plating liquid, use contains in the handled polymer elements of pressure fluid of high concentration catalyst composition, on the outmost surface of polymer elements since exist a large amount of plating catalyzer, plated film be easy to from outmost surface begin the growth.Therefore, have the weak part of closing force in the plated film, closing force is easy to produce uneven problem in chemical plating is handled.In addition, contain carbon dioxide pressurized chemical plating liquid and soak into, need high pressure to the catalyst component that is present in the polymer elements deep inside in order to make, the manufacturing installation that therefore essential sealed precision is high etc., the burden in the manufacturing is bigger.Therefore, consider industrial production, the utilization ratio of plating catalyzer that is scattered in polymer elements is still lower.Its result will use pressure fluid to come the dispersion treatment of dispersed catalyst composition to handle under the situation about combining the problem that exists cost to improve with the chemical plating of patent documentation 2.And, catalyst component is scattered under the situation of molten resin as patent documentation 1 is described by injection molding method, if use the pressure fluid that is dissolved with catalyst component with saturation concentration,, the pressure change in the cylinder separates out from pressure fluid easily because then soaking into before polymer elements at catalyst component.Because this catalyst component of separating out is not dissolved in pressure fluid, therefore can not soak into inside to polymer elements, become unnecessary catalyst component.In addition, because the plating catalyst concentration that will be dispersed to polymer elements of separating out of catalyst component reduces, inhomogeneous in the dispersion that becomes of polymer elements internal activator composition simultaneously, the change of closing force increased when the closing force of plated film reduced.Though be dissolved in the concentration of the catalyst component in the pressure fluid by reduction, can reduce separating out of aforesaid catalyst component, but owing to reduced the amount of introducing the catalyst component of polymer elements, there is the further problem that reduces of adaptation of plated film under this situation.

In addition, in the carbon dioxide pressurized chemical plating of the use of patent documentation 2 is handled, contain carbon dioxide pressurized and pure chemical plating liquid owing to use, must use with chemical plating liquid and as being contained in by the polymer elements of plating thing in the encloses container that energy is durable under high temperature and high pressure environment.Therefore and since the capacity limit of encloses container the quantity of the treatable polymer elements of institute once, the chemical plating processing must be batch treatment thus.Its result carries out the method that chemical plating handles and can not be applicable to continuous production processes as use as described in the patent documentation 2 is carbon dioxide pressurized, is difficult to expect high production.Therefore, after using pressure fluid formation to be dispersed with the polymer elements of catalyst component, be desirably in and carry out the chemical plating processing under the normal pressure, but under normal pressure, carry out as mentioned above under the situation of chemical plating processing, because chemical plating liquid can not fully soak into the inside to polymer elements, having plated film is that catalyst core is grown with the plating catalyzer of polymer elements outmost surface, and can not form the problem of the plated film with high closing force.

The present invention carries out in order to solve above-mentioned problem, the object of the present invention is to provide by utilizing the carbon dioxide pressurized polymer elements that will be dispersed with catalyst component under normal pressure, to carry out chemical plating and handle, and can make the manufacture method of the polymer elements of plated film with excellent adaptation.

Manufacture method with polymer elements of plating of the present invention comprises:

The catalyst component that use will contain the metal that becomes the plating catalyzer is dissolved in carbon dioxide pressurized pressure fluid, forms the dispersion steps of the polymer elements that is dispersed with described catalyst component,

The polymer elements that is dispersed with described catalyst component be impregnated in the pre-treatment step of pure treatment solution under normal pressure,

To carry out pretreated polymer elements by described pure treatment solution and under normal pressure, impregnated in the chemical plating step that the chemical plating liquid that contains alcohol forms plated film.

In above-mentioned manufacture method, catalyst component is scattered in the mode of resin molded body, above-mentioned dispersion steps can comprise by making above-mentioned pressure fluid contact the process that forms the polymer elements that is dispersed with above-mentioned catalyst component with resin molded body.In addition, in this mode, above-mentioned resin molded body can use flaky resin molded body.Further, in this mode, above-mentioned manufacture method can also comprise embedded formation step after above-mentioned dispersion steps, before the pre-treatment step, be about to the above-mentioned sheet polymer component configuration of catalyst component that is dispersed with in mould, injecting molten resin in above-mentioned mould, thus make above-mentioned sheet polymer parts and above-mentioned molten resin form one.

In above-mentioned manufacture method, catalyst component is scattered in the mode in the molten resin, above-mentioned dispersion steps can comprise makes above-mentioned pressure fluid contact with molten resin, the molten resin that is dispersed with above-mentioned catalyst component is passed through injection forming or extrusion molding, form the polymer elements that is dispersed with above-mentioned catalyst component.In addition, in this mode, above-mentioned dispersion steps can also comprise makes above-mentioned pressure fluid contact with the 1st molten resin, the 1st molten resin that is dispersed with above-mentioned catalyst component is injected in the mould, further, in the mould of having injected the 1st molten resin that is dispersed with above-mentioned catalyst component, injection does not contain the 2nd molten resin of catalyst component, forms the polymer elements that is dispersed with above-mentioned catalyst component in view of the above.In addition, in aforesaid way, it is organic solvent that above-mentioned pressure fluid can also contain fluorine.

Manufacturing method according to the invention, use pressure fluid under normal pressure, to utilize pure treatment solution to carry out pre-treatment catalyst component dispersive polymer elements, under normal pressure, utilize the chemical plating liquid that contains alcohol that above-mentioned pretreated polymer elements is carried out chemical plating and handle, can make the polymer elements of plated film in view of the above with excellent adaptation.In addition, according to above-mentioned manufacture method, even, also can form plated film with high closing force for the few polymer elements of catalyst component.In addition, according to above-mentioned manufacture method,, there is no need to use carbon dioxide pressurized chemical plating to handle owing to can both under normal pressure, carry out by the pre-treatment of pure treatment solution and arbitrary processing of chemical plating processing.Therefore, there is no need in chemical plating is handled, to use the bigger high withstand voltage manufacturing installation of burden on making, in industrial production, can make the polymer elements of plated film continuously with excellent adaptation.

Description of drawings

Fig. 1 is the concise and to the point sectional view of employed manufacturing installation in the related dispersion steps of the expression embodiment of the invention 1.

Fig. 2 is the concise and to the point mode chart of employed manufacturing installation in the related dispersion steps of the expression embodiment of the invention 2.

Fig. 3 is the employed concise and to the point mode chart that batches body in the related dispersion steps of the expression embodiment of the invention 2.

Fig. 4 is the concise and to the point sectional view of expression with the major portion of the state of sheet polymer component configuration in mould for the concise and to the point sectional view of the major portion of the state of the related embedded forming step of the expression embodiment of the invention 2: Fig. 4 (A), and Fig. 4 (B) is for being illustrated in the concise and to the point sectional view of injecting the major portion of the state that is filled with molten resin mould in.

Nomenclature

100 pressure fluid supply units

200 injection forming portions

250 mold

300 fluid supply units

400 autoclaving portions

L flaky resin molding

M sheet polymer parts

Embodiment

Below, be specifically described for the manufacture method with plated film polymer elements of present embodiment.

The manufacture method of the polymer elements with plated film of present embodiment, comprise dispersion steps, in this dispersion steps, use the pressure fluid that in carbon dioxide pressurized, dissolves the catalyst component that contains the metal that becomes the plating catalyzer, form the polymer elements that is dispersed with catalyst component.Also can make catalyst component be scattered in polymer elements by using the pressure fluid plating catalyzer that in carbon dioxide pressurized, dissolves the catalyst component that contains the metal that becomes the plating catalyzer, need not use the etching solution that contains the big sexavalence chromic acid of carrying capacity of environment etc. to carry out etch processes.In addition, carbon dioxide pressurized than using, owing to can make catalyst component soak into inside,, also can handle by chemical plating as described later and form plated film even for polymer elements by the resin formation that does not contain etching composition to polymer elements.

As catalyst component,, there is not special restriction so long as in dispersion steps, have solvability in carbon dioxide pressurized, contain the metal that in the chemical plating step, becomes the plating catalyzer and get final product.Particularly, can enumerate the particulate of metals such as containing palladium, platinum, nickel, copper, silver, contain the complex compound of above-mentioned metal, and the modifiers such as oxide compound of metal complex.Wherein, preferably for the metal complex of carbon dioxide pressurized solvability excellence.As this type of catalyst component, for example can enumerate nickelocene, two (methyl ethyl diketone) palladium (II), dimethyl (cyclooctadiene) platinum (II), hexafluoroacetylacetone palladium (II), hexafluoroacetylacetone and close copper (II), hexafluoroacetylacetone platinum (II), hexafluoroacetylacetone (trimethyl-phosphine) silver (I), dimethyl (seven fluorine acetyl caproyl acid) silver (AgFOD) and above-mentioned modifiers such as oxide compound.Above-mentioned substance can use separately also and can multiple mixing use.Wherein, containing with the fluorine atom is the metal complex of part owing to have excellent solvability for carbon dioxide pressurized, so preferred.Need to prove, metal complex is after being scattered in polymer elements, though owing to the heat in the manufacturing installation etc. is reduced, existence is scattered in the situation of polymer elements as metal simple-substance, but is fixed on the inside of polymer elements by above-mentioned reduction can will become the plating catalyzer when chemical plating is handled metallics.Therefore, even before the chemical plating step be that the catalyst component of above-mentioned metal simple-substance state is scattered in polymer elements and also can with sex change.

As carbon dioxide pressurized, can use the carbon dioxide pressurized of liquid state, gaseous state or supercritical state.Pressure is high more, and then the solubleness of the catalyst component in carbon dioxide pressurized is high more.Therefore, a large amount of catalyst components is scattered in the existing chemical plating processing of polymer elements, uses supercritical carbon dioxide at needs.Yet, according to the manufacture method of present embodiment, though since the polymer elements that uses lower concentration dispersed catalyst composition as the plated film that also can be formed the adaptation excellence by the plating thing, can use not to be the carbon dioxide pressurized of supercritical state.Therefore, carbon dioxide pressurized promptly can the use is forced into the above carbonic acid gas of stagnation point (temperature is more than 31 ℃, pressure is the above supercritical state of 7.38MPa), also can use the carbonic acid gas of the pressure that is forced into subcritical point.More specifically, carbon dioxide pressurized pressure is preferably 5-30MPa, and temperature is preferably 10-150 ℃.Under the situation of insufficient pressure 5MPa, the tendency that exists carbon dioxide pressurized density to reduce.On the other hand, be higher than when pressure under the situation of 30MPa, need high withstand voltage equipment in the manufacturing installation, cost uprises.In addition, under the situation of 10 ℃ of temperature less thaies, there is the tendency of the dispersiveness reduction of catalyst component.On the other hand, temperature is higher than under 150 ℃ the situation, has the sealing of manufacturing installation to become difficult tendency.In addition, carbon dioxide pressurized density is preferably 0.10-0.99g/cm ³

When preparation is dissolved in catalyst component pressure fluid in carbon dioxide pressurized, can use existing known method.For example, Liquid carbon dioxide is pressurizeed, carbon dioxide pressurized being supplied to dropped into the dissolving tank that catalyst component is arranged, by mixing this catalyst component and the carbon dioxide pressurized pressure fluid for preparing by pressurization means such as pumps.Catalyst component concentration in the pressure fluid can be saturation concentration, but in the manufacture method of present embodiment, and the concentration of catalyst component is that its effect is bigger under the situation of lower concentration of not enough saturation concentration.Therefore, can reduce the introducing amount that does not participate in plating catalyst for reaction composition.In addition, because the concentration of the catalyst component in the pressure fluid is lower,, also can reduce separating out of catalyst component even when using injection molding method or extrusion molding method to be scattered in catalyst component in the molten resin, pressure change takes place.Therefore, according to the manufacture method of present embodiment, when economy can be improved, can cross the polymer elements that is dispersed with catalyst component equably.Further, if the catalyst component concentration in the pressure fluid is lower concentration, the amount that is attached to the catalyst component of polymer elements outmost surface also tails off.Therefore, can be suppressed at the plated film that outmost surface forms low pinning effect.

In the present embodiment, utilize injection molding method or extrusion molding method to make under the shaping preceding molten resin and the contacted situation of pressure fluid, it is organic solvent that this pressure fluid can also contain fluorine.By using fluorine is organic solvent, in dispersion steps, catalyst component is disperseed efficiently at the near surface of polymer elements.In addition, have excellent thermotolerance, contain the pressure fluid that this fluorine is an organic solvent, can be suppressed at the decomposition that pyritous contacts the catalyst component when mixing by use because fluorine is an organic solvent.Therefore, be exposed under the situation of the heat in the manufacturing installation with catalyst components such as metal complexs before molten resin contacts, can suppress the thermal reduction of metal simple-substance, and then can efficiently catalyst component be scattered in polymer elements at pressure fluid.Further, under the situation of preparation pressure fluid, above-mentioned carbon dioxide pressurized being supplied to dropped into the dissolving tank that catalyst component is arranged, under high pressure it is mixed and stir, therefore under the situation of making pressure fluid again, supply passageway must be reduced pressure for the moment and catalyst component is supplied to dissolving tank.With respect to this, be organic solvent if use fluorine, can under normal pressure, prepare catalyst component is dissolved in the mixed solution that fluorine is an organic solvent, then can pass through itself and carbon dioxide pressurized the mixing in pipe arrangement are prepared pressure fluid to this mixed solution pressurization.Therefore, need not also there is no need in order to be dissolved in new catalyst component carbon dioxide pressurized and dissolving tank to be reduced pressure for mixed catalyst composition and carbon dioxide pressurized and use the high pressure dissolving tank.Need to prove, using above-mentioned fluorine is under the situation of organic solvent, preferably be that organic solvent mixes and prepare mixed solution,, thereby the mixed solution and carbon dioxide pressurized mixing of pressurization prepared pressure fluid the mixed solution pressurization of gained with catalyst component and fluorine.

As fluorine is organic solvent, does not have special restriction, can enumerate perfluorinated alkyl amine, perfluorinated alkyl polyether carboxylic acid, perfluorination alkane, fluorine atom class interfacial agent etc.Can use above-mentioned substance separately, also can a plurality of mixing use.In above-mentioned substance, preferred use low price, perfluorinated alkyl amine such as solvability excellence, perfluorination tripropylamine, perfluorination tributylamine, perfluorination three amylamines in carbon dioxide pressurized with high heat resistance (the expectation boiling point is more than 150 ℃).Using fluorine is catalyst component concentration in the mixed solution under the organic solvent situation, owing to depend on employed catalyst component or fluorine is the kind of organic solvent, does not have special restriction, but is preferably 0.01-10 quality %.

The resin material that constitutes the polymer elements that is dispersed with catalyst component is arbitrarily, can use thermoplastic resin, thermosetting resin and ultraviolet curing resin.Wherein, be preferably thermoplastic resin.The kind of thermoplastic resin is arbitrarily, can be suitable for amorphism, crystalline any.For example, can use synthon, polypropylene, polyamide-based resin, polymethylmethacrylate, polycarbonate, amorphous polyolefin, polyetherimide, polyethylene terephthalate, liquid crystalline polymers, ABS such as polyester is Biodegradable plastics, nylon-based resin etc. such as resin, polyamidoimide, polyphthalamide, polyphenylene sulfide, poly(lactic acid) and above-mentioned matrix material.In addition, can use the mixing resin material that glass fibre, carbon fiber, nano-sized carbon, mineral substance etc., various inorganic fillers etc. are arranged.

Be dispersed with the polymer elements of catalyst component, can contact with above-mentioned pressure fluid by the resin molded body that makes shaping forms, and also can make the molten resin before being shaped contact and form with above-mentioned pressure fluid.Being the form of the plated body in the dispersed catalyst composition, himself can be the molding of net shape, also can be the molten resin before forming set shape.Further, also can be processed afterwards intermediates such as sheet material.Use under the situation of resin molded body, its shape does not have particular restriction,, particulate state tabular except heavy-walled, the tubulose, can be the arbitrary shapes such as sheet with thin-walled.For example, when the light path of the employed f θ of photoscanning mirror, projection TV bends employed large-scale mirror etc. in the light reflector of making the headlight assembly reflector always utilize vapour deposition method etc. or laser beam printer or duplicating machine etc., can utilize the manufacture method of present embodiment.Under the situation of using the flaky resin molding, its thickness does not have special restriction, but is preferably 10-200 μ m.When thickness is 10 μ m when above, can guarantee physical strength.On the other hand,, utilizing under the embedded moulding method situation of film, can prevent that flaky resin molded body from floating from mould when thickness is 200 μ m when following.

In dispersion steps, form the method for the polymer elements that is dispersed with catalyst component, get final product, do not have special restriction so long as catalyst component can be scattered in polymer elements.Catalyst component is scattered under the situation of resin molded body, for example, resin molded body can be contained in high withstand voltage encloses container, to the encloses container supply catalyst component is dissolved in carbon dioxide pressurized pressure fluid, by resin molded body is contacted with pressure fluid, thereby obtain being dispersed with the polymer elements of catalyst component.Catalyst component is scattered under the situation of flaky resin molded body, also the flaky resin molding can be contained in high pressure vessel across the barrier film that is formed by the inorganics coiling body that forms of reeling.As the above-mentioned barrier film that is formed by inorganics, particularly, for example, mesh sheets, the SUS that can enumerate aluminum make mesh sheets, woven fiber glass etc.Because pressure fluid can pass through above-mentioned barrier film, the pressure fluid that diffustivity is high spread equably by barrier film soak in flaky resin molded body all.In view of the above, the destructive while can be reduced, catalyst component polymer elements can be scattered in the aggegation less state resulting polymer elements.

In addition, thereby catalyst component is scattered under the situation that molten resin forms the polymer elements be dispersed with catalyst component, for example, in manufacturing installation, make and catalyst component is dissolved in carbon dioxide pressurized pressure fluid contacts with molten resin, and make catalyst component be scattered in molten resin, by being desirable shape, can access the polymer elements that is dispersed with catalyst component with this molten resin injection forming or extrusion molding.Utilize above-mentioned injection molding method or extrusion molding method since can be in molten resin direct dispersed catalyst composition, when being shaped, can form the polymer elements that is dispersed with catalyst component.Particularly, utilize above-mentioned injection molding method or extrusion molding method catalyst component to be scattered under the situation of molten resin, catalyst component soaks into the deep inside to polymer elements owing to conducting oneself with dignity, the catalyst component of the near surface of polymer elements becomes lower concentration.Therefore, use under the situation of the pressure fluid that contains the lower concentration catalyst component, the catalyst component concentration of near surface further reduces.Therefore, though handle the plated film that can not form the adaptation excellence by existing chemical plating, but manufacture method according to present embodiment, even lower concentration ground dispersed catalyst composition in above-mentioned molten resin, by pre-treatment step described later is combined with the chemical plating step, can form the plated film of adaptation excellence.

Utilize above-mentioned injection molding method or extrusion molding method catalyst component to be scattered under the situation of molten resin, pressure fluid contacts with molten resin, both can be in the plasticization cylinder, also can be to carry out at mould or extrusion die inside.Further, utilizing under the situation of injection molding method, can use so-called sandwich moulding method in order to form molding with cortex and core.Particularly, can will be injected into mould as above-mentioned the 1st molten resin that is dispersed with catalyst component, injection does not contain the 2nd molten resin of catalyst component in this has the mould of the 1st molten resin, thereby forms the polymer elements with cortex and core.According to this moulding method, can make the polymer elements that is dispersed with catalyst component than the cortex on inner surface with greater concn.The the 1st and the 2nd resin can use resin of the same race, but by using 2nd resin different with the 1st resin, can realize the high strength or the lightness of polymer elements.Need to prove,, can use above-mentioned thermoplastic resin as the 1st and the 2nd resin.

Though can form the polymer elements that is dispersed with catalyst component by above-mentioned dispersion steps, in the present embodiment, have in formation under the situations such as polymer elements of metallic reflective coating, the sheet polymer parts that are dispersed with catalyst component can be set in mould, injecting molten resin in this mould further makes the incorporate embedded shaping of sheet polymer parts and molten resin.In view of the above, can make sheet polymer parts and molten resin integrated, thereby can form local by the polymer elements of high performance.In addition, the sheet polymer parts are arranged under the situation in the mould, the sheet polymer parts that are complementary of the interior shape of preliminary shaping and mould also can make the driving fit of sheet polymer parts in mould before the molten resin of the embedded shaping of injection in advance.

Then, carry out the above-mentioned polymer elements that is dispersed with catalyst component be impregnated in the pre-treatment step of pure treatment solution under normal pressure.Contain the chemical plating step of the chemical plating liquid of alcohol by this pre-treatment step and use after this,, also can form the plated film of adaptation excellence even under normal pressure, the polymer elements that is dispersed with the lower concentration catalyst component is carried out the chemical plating processing.Its reason is not also understood now.Yet, think that according to the inventor's etc. research it is because following effect, promptly carry out pre-treatment by pure treatment solution by the polymer elements that will be dispersed with catalyst component, alcohol soaks into the inside to polymer elements, the near surface swelling of polymer elements, the free volume of resinous principle increases, even chemical plating liquid also is easy to soak into to polymer elements inside under normal pressure in chemical plating step after this, and be spilled near surface owing to the alcohol that soaks into makes the catalyst component that is scattered in polymer elements inside, thereby the catalyst component concentration of near surface increases.Promptly, the polymer elements that does not use the pre-treatment of pure treatment solution and will be dispersed with the lower concentration catalyst component impregnated in the chemical plating liquid that contains alcohol under normal pressure carries out under the situation that chemical plating handles, also can only form the low plated film of closing force even confirmed not form on the polymer elements surface plated film or formed plated film.This can think because less in the amount of the near surface plating catalyzer of polymer elements, can not form plated film, even if or can form plated film, be the catalyst core plated film of growing only also, and can not obtain the physical property pinning effect of enough plated films with the catalyst component of near surface.In addition, use the pressure fluid that contains palladium complex as catalyst component, the polymer elements by polyamide-based resin formation that is dispersed with this catalyst component be impregnated in contain 1, under the situation in the pure treatment solution of 3-butyleneglycol, the weight of polymer elements increases, and has confirmed the swelling of polymer elements.Further, with the polymer elements after just handling by this alcohol treatment solution, place the polymer elements of certain hour after the processing at normal temperatures, thereby and in order to get rid of because the influence that the sex change of catalyst component produces and after processing, carry out the polymer elements that vacuum-drying reduces inner pure impregnation amount at normal temperature, utilize the chemical plating liquid that contains alcohol to carry out at normal temperatures under the situation of chemical plating processing respectively, the growth time of having confirmed plated film is in proper order for placing the polymer elements of certain hour at normal temperatures, polymer elements after just having handled, reach the polymer elements that reduces the impregnation amount of alcohol by vacuum-drying.Reduced the polymer elements of pure impregnation amount by vacuum-drying, handle the back and can think than firm, cause the reduction of swelling effect owing to soak into to the minimizing of the alcohol of polymer elements inside in the slow reason of growth time that normal temperature is placed the polymer elements plated film of certain hour.On the other hand, alcohol is contained be dipped under the situation by the resin molded body of polyamide-based resin formation, soak into to the pure impregnation amount of inside and behind certain hour, reach capacity.In addition, 1,3 butylene glycol volatilization hardly at normal temperatures.Therefore, the polymer elements after just having handled, place any of polymer elements of certain hour at normal temperatures,, can think roughly the same by the swelling degree of pure treatment solution for contain the state that is soaked with alcohol in inside.Moreover, the reason of these the 2 kinds plated film growth time differences that sample produced can be speculated as, except that the swelling effect, owing to place the near surface that catalyst component is spilled over to polymer elements more.Therefore, can think because this swelling effect, utilization after this contains in the chemical plating processing of pure chemical plating liquid, and chemical plating liquid easily soaks into to the polymer elements that contains the state that is soaked with alcohol, uprises in the concentration of the catalyst component of near surface owing to spill-over effects simultaneously.Its result can infer, handles even the polymer elements that is dispersed with a spot of catalyst component is carried out chemical plating under normal pressure, also can form the plated film of adaptation excellence.

As the alcohol that is used for pure treatment solution, particularly, for example be preferably and be selected from ethanol, 1-propyl alcohol, 2-propyl alcohol, 1,2-butyleneglycol, 1,3-butyleneglycol, 2-methyl-2, any one of 4-pentanediol, 2-(2-butoxy oxyethyl group) ethanol, 2-(2 diethoxy) ethanol, 2-(2-methoxy ethoxy) ethanol, ethylene glycol, glycol ether, TEG, polyoxyethylene glycol and glycol polypropylene.Wherein, consider impregnability,, more preferably have the following capillary alcohol of 50dyn/cm preferably at 20 ℃ of lower capillary alcohol of surface tension (73dyn/cm) that have than water to polymer elements.Further, consider the security in the manufacturing, preferably have the alcohol of the point of ignition more than 40 ℃.As aforesaid alcohol with low surface tension and high point of ignition, for example can enumerate 1,3-butyleneglycol (surface tension: 37.8dyn/cm, point of ignition: 121 ℃), 2-methyl cellosolve (surface tension: 31.8dyn/cm, point of ignition: 43 ℃), 2-(2-methoxy propoxy) propyl alcohol (surface tension: 28.8dyn/cm, point of ignition: 74 ℃) etc.Wherein, the more preferably 1,3 butylene glycol of impregnability excellence.

The alcohol treatment solution as long as contain alcohol at least, can also contain other solvents that mix with the alcohol that uses, for example water.But if the content of other solvents is too many, the growth needs of plated film is long-time sometimes when chemical plating is handled.Therefore, pure content is preferably more than the 50vol%, more preferably more than the 90vol% in the pure treatment solution.Particularly, at the preferred pure treatment solution that except the impurity of unavoidably sneaking into, only contains alcohol in fact under the situation of mechanicals.Need to prove, can contain additive for the impregnability that improves polymer elements in the pure treatment solution.As above-mentioned additive, particularly can enumerate interfacial agent.

By the pre-treatment of pure treatment solution, can under normal pressure, carry out as mentioned above.Therefore, need not to use high price manufacturing installations such as high pressure vessel and can handle continuously.Need to prove, in this manual, be meant under the so-called normal pressure under the atmosphere that does not have pressurization.Treatment time is owing to according to the kind of polymer elements or pure kind and difference do not have special restriction, still be preferably 1 fen～2 hours.If the treatment time is too short, alcohol can not fully soak into to polymer elements, can not obtain enough effects by pure treatment solution generation.On the other hand,, not only make efficient and reduce, also exist because the situation of the resin structure reduction of the polymer elements that alcohol causes if the treatment time is long.In addition,, can carry out at normal temperatures, carry out in order to promote pure treatment solution to contain to be dipped in polymer elements also can heat by the pre-treatment that pure treatment solution carries out.Under the situation of heating, according to rerum natura such as the boiling point of employed alcohol and difference, but treatment temp is preferably more than the second-order transition temperature of the resin that constitutes polymer elements.If more than the second-order transition temperature of treatment temp for the resin of formation polymer elements, polymer elements takes place by the plastic degeneration, pure treatment solution is easy to soak in polymer elements.

In the present embodiment, after above-mentioned pre-treatment step, before the chemical plating step, the additional reductive agent step of handling polymer elements by the reductive agent aqueous solution that contains reductive agent can also be set.In view of the above, reductive agent is soaked into to polymer elements inside, and make that in chemical plating step after this reduction of metal ion in the chemical plating liquid is further successfully carried out.In order to improve the impregnability to polymer elements, the reductive agent aqueous solution can also contain alcohol.But if pure content is too much, the solubleness of reductive agent reduces.Therefore pure content preferably is discontented with 50vol%.As reductive agent, can use the reductive agent identical reductive agent used with chemical plating liquid.Particularly, for example can enumerate at least a kind that is selected from Hypophosporous Acid, 50, sodium hypophosphite, dimethylamine borane, hydrazine, formaldehyde, sodium borohydride and the phenols.Particularly, forming under the situation of Ni-P plating, reductive agent is preferably selected from least a in Hypophosporous Acid, 50 and the sodium hypophosphite.

Then, under normal pressure, impregnated in the chemical plating liquid that contains alcohol by the pretreated polymer elements of pure treatment solution, carry out on polymer elements, forming the chemical plating step of plated film aforesaid.In the manufacture method of present embodiment, in above-mentioned pre-treatment step, carried out pre-treatment by pure treatment solution owing to be dispersed with the polymer elements of catalyst component, can form the plated film that can obtain high pinning effect.In addition, make chemical plating liquid contain the surface tension that alcohol has reduced chemical plating liquid, even therefore normal pressure chemical plating processing down, chemical plating liquid also can successfully soak in polymer elements.Further, alcohol is had an effect as the reductive agent that postpones the plated film growth, so chemical plating liquid can postpone the plating reaction on the outmost surface in the surface portion of polymer elements begins to soak into.Its result, by the plated film that this manufacture method forms, the interior surface growth at polymer elements has higher adaptation.

The chemical plating step can be carried out under normal pressure as mentioned above.Under the existing situation of thereby carbon dioxide pressurized and chemical plating liquid mechanical stirring being used the bath that mixes forcibly, because pressure or temperature variation are difficult to stably prepare uniform plating bath.Therefore, chemical plating is handled under the situation of a plurality of polymer elements, is easy to take place the change of plating reaction at the surface portion of each polymer elements.Its result, the dhering strength of plated film is easy to take place cataclysm.Thus, for example, in thermal cycling test, exist the adaptation of plated film to be easy to reduce, the part of plated film is easy to peel off or the problem of defective such as expansion.With respect to this, according to the manufacture method of present embodiment, can prepare chemical plating liquid at normal pressure, can suppress the change of plating reaction, can form the few plated film of closing force change.

And, under normal pressure, polymer elements be impregnated in chemical plating liquid, for example, the chemical plating liquid that will contain alcohol is contained in the open container, by polymer elements being impregnated in this open container, can implement chemical plating and handle.Therefore, need not to use the high withstand voltage encloses container under the carbon dioxide pressurized situation of existing use, can carry out chemical plating thus continuously and handle.Therefore, the manufacture method of present embodiment is suitable for continuous production processes.

As the alcohol that is mixed in the chemical plating liquid, can use and the identical alcohol of the employed alcohol of above-mentioned pre-treatment.Wherein, the preferred 1,3 butylene glycol that uses with low surface tension and high point of ignition.Pure content in the chemical plating liquid is any, owing to change so do not have special restriction according to employed pure kind optimum content, but be preferably 20-60vol%.

As the employed plating liquid of chemical plating liquid, can use always known plating liquid.Particularly, for example, can enumerate nickel phosphor plating and cover liquid, nickel boron plating liquid, palladium plating liquid, copper plating liquid, silver-colored plating liquid, cobalt plating liquid etc.Need to prove, use the above-mentioned chemical plating liquid that contains alcohol to carry out after chemical plating handles, further stacked plated film or the electroplating film that utilizes existing water system chemical plating liquid on this plated film.Treatment temp in the chemical plating step so long as above the getting final product of temperature that plating reacts can be taken place, does not have special restriction, but in order to promote soaking into of chemical plating liquid, is preferably more than the second-order transition temperature of the resin that constitutes polymer elements.

Below, be elaborated by providing embodiment for the present invention, but the present invention is not limited to these embodiment.

Embodiment 1

In the present embodiment, be dissolved with catalyst component and fluorine is the pressure fluid of organic solvent in carbon dioxide pressurized for using, the method that forms plated film by sandwich moulding method on the polymer elements that is dispersed with catalyst component that forms describes.Need to prove, in the present embodiment, as the resin that forms cortex and core, all use crystalline thermoplastic resin polyamide 66 (エ of Mitsubishi Application ジニアリ Application グプラスチ Star Network society system, 3010R).In addition, using hexafluoroacetylacetone palladium (II) complex compound as catalyst component, is that organic solvent uses perfluorination triamylamine (シ Application Network レストラボラトリ one society's system, molecular formula: C15F33N, molecular weight: 821.1, boiling point: 220 ℃) as fluorine.

Dispersion steps

Fig. 1 is used to form the concise and to the point sectional view of the employed manufacturing installation of polymer elements that is dispersed with catalyst component in the present embodiment for expression.As shown in Figure 1, this manufacturing installation has pressure fluid supply unit 100 and injection forming portion 200, wherein will to be dissolved with catalyst component and fluorine in carbon dioxide pressurized be that the pressure fluid of organic solvent is supplied with the 1st plasticity-cylinder 210 to pressure fluid supply unit 100, injection forming portion 200 has the 1st plasticity-cylinder 210 that is used to form cortex, is used to form the 2nd plasticity-cylinder 240 and the mold 250 of core.Above-mentioned pressure fluid supply unit 100 and injection forming portion 200 carry out work control by the control device that does not illustrate in the drawings.

Pressure fluid supply unit 100 has Liquid carbon dioxide gas cylinder 101, be used to supply with Liquid carbon dioxide is forced into set pressure carbon dioxide pressurized carbonic acid gas with syringe pump 102 be used to prepare, supply with catalyst component is dissolved in the formulations prepared from solutions portion 110 that fluorine is the mixed solution C of organic solvent.At pipe arrangement that Liquid carbon dioxide gas cylinder 101 and carbonic acid gas are connected with syringe pump 102 and carbonic acid gas with being respectively arranged with suction on syringe pump 102 and the pipe arrangement that formulations prepared from solutions portion 110 is connected with air control valve 104 with supply with air control valve 105.In addition, carbonic acid gas has not shown water cooler with syringe pump 102, is set temperature with carbon dioxide pressurized temperature regulation thus.Catalyst component is dissolved in fluorine is the tempering tank 111 that organic solvent is made mixed solution C thereby formulations prepared from solutions portion 110 has, thereby and the solution syringe pump 112 that is used for mixed solution C is forced into set pressure liquor charging, wherein, at pipe arrangement that tempering tank 111 and solution are connected with syringe pump 112 and solution with being respectively arranged with suction on syringe pump 112 and the pipe arrangement that the 1st plasticity-cylinder 210 is connected with air control valve 114 and supply with air control valve 115.In the present embodiment, the concentration that has prepared catalyst component is the mixed solution of 1.0 quality %.

Under the situation of preparation pressure fluid, be that organic solvent mixes stirring under normal temperature, normal pressure with catalyst component and fluorine at first at tempering tank 111, preparation mixed solution C.Then, open solution with the suction of syringe pump 112 1 sides with air control valve 114, at normal temperatures from tempering tank 111 by strainer 113 suction mixed solution C, with the pressure-controlling of syringe pump 112 mixed solution C is forced into set pressure by solution.In the present embodiment, mixed solution C is forced into 10MPa.On the other hand, under the state of opening manual valve 106, by filter screen 107 pumping liquid carbonic acid gas, and with the pressure-controlling of syringe pump 102 Liquid carbon dioxide is forced into set pressure by carbonic acid gas from Liquid carbon dioxide gas cylinder 101.In the present embodiment, from the Liquid carbon dioxide of Liquid carbon dioxide gas cylinder 101 suction 4-6MPa, to this by carbonic acid gas with syringe pump 102 pressurizations, be 10 ℃ carbon dioxide pressurized thereby supply pressure is 10MPa, temperature.And, can stably supply with carbon dioxide pressurized by measuring highdensity Liquid carbon dioxide at low temperatures.

When pressure fluid being supplied with the 1st plasticity-cylinder 210, close suction with air control valve 104,114, open supply with usefulness air control valve 105,115 after, carbonic acid gas is changed to flow control with syringe pump 112 from pressure-controlling with syringe pump 102 and solution, by control carbonic acid gas syringe pump 102 and the solution actuating speed (flow) and the driving time of the tube of syringe pump 112, thereby make the mixed solution C of pressurization and carbon dioxide pressurized flowing reach set throughput ratio.Thus, in pipe arrangement with mixed solution C and carbon dioxide pressurized mixing.In the present embodiment, mixed solution C and carbon dioxide pressurized throughput ratio are set at 1: 10.As mentioned above make the blended pressure fluid with set throughput ratio mobile state under, corresponding to from the triggering signal of mold 250 fluid supplying opening 218, a certain amount of pressure fluid is supplied with the 1st plasticity-cylinder 210 by open importing valve 212 described later.Behind flow control supply pressure fluid, stop carbonic acid gas for the moment with syringe pump 102 and solution syringe pump 112, close to supply with and use air control valve 105,115.Then, carbonic acid gas is transformed to pressure-controlling from flow control with syringe pump 102 and solution once more with syringe pump 112, with similarly above-mentioned, from Liquid carbon dioxide gas cylinder 101 pumping liquid carbonic acid gas, from tempering tank 111 suction mixed solution C, and pressurization respectively, and then standby.Further, corresponding to triggering signal, supply with pressure fluid by above-mentioned flow control from mold 250.By repeating aforesaid operations, desultory pressure fluid is supplied to the 1st plasticity-cylinder 210.In the present embodiment, from being open into of the fluid supplying opening 218 that imports valve 212 supply with finish between, the pressure that is detected by pressure warning unit 260 is supplied with the 1st plasticity-cylinder 210 by spells with pressure fluid in the 8-10MPa scope.In addition, in the present embodiment, the feed rate of control pressure fluid, making in the polymer elements of injection forming institute's dispersed catalyst become component is 100ppm.As mentioned above, because the pressure fluid of present embodiment contains the lower concentration catalyst component, even the pressure in the plasticity-cylinder 210 change, can prevent that catalyst component from from the separating out of pressure fluid, can form the polymer elements that catalyst component is evenly dispersed simultaneously.Need to prove that the amount of catalyst component is calculated the consumption that per 1 injection is dissolved with the pressure fluid that belongs to complex compound from solution with the consumption of the high pressure mixing liquid in the syringe pump 112, converses the consumption of the metal complex of per 1 injection thus.

In the upper side of the 1st plasticity-cylinder 210, from upstream side begin to set gradually be useful on the 1st resin that the 1st resin is supplied with the 1st plasticity-cylinder 210 supply with hopper 211, be used to supply with pressure fluid importing valve 212, be used for the carbon dioxide pressurized ventilation opening 213 of discharges in the 1st plasticity-cylinder 210.In addition, with importing valve 212 position in opposite directions of the lower side of the 1st plasticity-cylinder 210 and with ventilation opening 213 position in opposite directions be respectively arranged be used to detect in the pressure warning unit 215,216 and the not shown temperature sensor of pressure.This importing valve 212 has fluid supplying opening 218 at the base end part that is connected with the 1st plasticity-cylinder 210, has the piston 217 of importing simultaneously in inside, by opening fluid supplying opening 218, supply with pressure fluid to the 1st plasticity-cylinder 210 from pressure fluid supply unit 100 by importing piston 217.In addition, ventilation opening 213 is connected by vapor pipe across buffer container 219 and vacuum pump 220, and by opening ventilation opening 213, making vacuum pump 220 work, the inside of the 1st plasticity-cylinder 210 is depressurized.Therefore, in the 1st plasticity-cylinder 210, from importing near the valve 212 between near the ventilation opening 213, by the high pressure pressure fluid, pressure fluid and the 1st molten resin are touched mixing with pressurized state.Need to prove,, be provided with the 2nd resin supply hopper 241 that is used for the 2nd resin is supplied with the 2nd plasticity-cylinder 240 in the upper side of the 2nd plasticity-cylinder 240.

Driving side end at the 1st and the 2nd screw rod S1, S2 is connected with not shown motor respectively.By heated plasticity-cylinder 210,240 by the band well heater (not shown) of the outside wall surface that is arranged at plasticity-cylinder 210,240, by screw rod S1, S2 to supply with from each resin the resin that is supplied to hopper 211,241 carry out mixing, dissolve.In addition, the injection side end of the 1st and the 2nd plasticity-cylinder 210,240 is connected to the spray nozzle part 230 that is communicated with mold 250 interior cavitys 253.And since during milling the front end of spray nozzle part 230 be closed, by the 1st and the 2nd molten resin being expressed into the place ahead of the 1st and the 2nd screw rod S1, S2 respectively, the 1st and the 2nd screw rod S1, S2 retreat.Begin metering thus.And after the plasticization metering, by back pressure screw rod S1, S2 in each plasticity-cylinder 210,240 are advanced, in cavity 253, inject the 2nd molten resin that filling is dispersed with the 1st molten resin of catalyst component and does not contain catalyst component respectively thus from spray nozzle part 230.In the present embodiment, be to disperse under in the 220-240 ℃ of scope in the temperature that temperature sensor detected of each plasticity-cylinder 210,240.Need to prove, catalyst component is scattered under the situation of molten resin, preferably under above-mentioned hot environment, carry out dispersion steps.

As shown in Figure 1, mold 250 has fixed mould 251 and moveable die 252, because fixed mould 251 and moveable die 252 connect, forms the cavity 253 of set shape in mold 250.As mentioned above, cavity 253 and spray nozzle part 230 are connected, and fill the 1st molten resin that is dispersed with catalyst component and the 2nd molten resin that does not contain catalyst component from this spray nozzle part 230 to cavity 253 injections.Fixed mould 251 and moveable die 252 are individually fixed in stationary platen 254 and movable platen 255, drive movable platen 255 by clamping mechanism, open and close mold 250 thus.In the present embodiment, use the mold 250 that forms 2 discoid moldinies simultaneously.Under the situation that forms cortex, the 1st molten resin injection of plasticization being measured from the 1st plasticity-cylinder 210 is filled to cavity 253.At this moment, the injection loading level is adjusted to the 1st molten resin does not have degree whole in the cavity filling 253.

On the other hand, in filling, with hopper 241 the 2nd resin is supplied with the 2nd plasticity-cylinder 240, carry out the plasticization metering by the 2nd screw rod S2 from the supply of the 2nd resin by the injection of above-mentioned the 1st plasticity-cylinder 210.At this moment, in the 2nd plasticity-cylinder 240, the 2nd resin that is not dispersed with catalyst component is melted.And just before the injection end-of-fill of the 1st molten resin that is dispersed with catalyst component, finish the plasticization metering of the 2nd molten resin.

Then, behind the injection end-of-fill of the 1st molten resin that is dispersed with catalyst component, the 2nd screw rod S2 is advanced, the 2nd molten resin injection that does not contain catalyst component is filled to cavity 253.At this moment, be filled in the stuffing pressure of the 1st molten resin that is dispersed with catalyst component of cavity 253 before, and given as security to the die surface that constitutes cavity 253 owing to the 2nd molten resin.Its result after the injection of the 2nd molten resin finishes, forms the layer with the 1st resin that is dispersed with catalyst component at the cortex of polymer elements, forms the layer with the 2nd molten resin that does not contain catalyst component at the core of molding.Behind the injection end-of-fill, cooling die portion 250, the resin of cooling curing inside can access the polymer elements that is dispersed with catalyst component by opening mold 250.

Pre-treatment step

Then, the formed polymer elements that is dispersed with catalyst component as mentioned above be impregnated in pure treatment solution, carry out pre-treatment.In the present embodiment, use treatment solution (a)～(h) shown in the following table 1.Need to prove, as a comparative example, in treatment solution (h), only make water.Each treatment solution is dropped in the open container, under the temperature under normal pressure, shown in the table 1 polymer elements was flooded wherein 30 minutes, carry out pre-treatment.According to the treatment solution difference and the change process temperature is because the boiling point and the point of ignition difference of each treatment solution.

Table 1

Treatment solution	Kind	Treatment temp (℃)
			(a)	1,3 butylene glycol	100
(b)	Ethylene glycol	100
			(c)	Macrogol 200	120
(d)	2-methyl-2, the 4-pentanediol	100
			(e)	The mixed treating liquid of 1,3 butylene glycol and Macrogol 200 (volume ratio: 1/1)	100
(f)	The mixed treating liquid of 1,3 butylene glycol and water (volume ratio: 1/1)	90
			(g)	The mixed treating liquid of Macrogol 200 and water (volume ratio: 1/1)	90
(h)	Water	90

The plated film step

Then, will carry out above-mentioned pretreated polymer elements and under normal pressure, impregnated in the chemical plating liquid that contains alcohol, and carry out chemical plating and handle.In the present embodiment, use chemical plating liquid (the pure content in the chemical plating liquid: 50vol%) that 1,3 butylene glycol and the nickel-phosphor bath (wild pharmaceutical industry difficult to understand) that contains metal-salt, reductive agent and the complexing agent of single nickel salt are mixed with.Above-mentioned chemical plating liquid is dropped in the container, with the polymer elements dipping wherein, under normal pressure, carry out chemical plating (sample 1～8) under 70～90 ℃ the temperature.In addition, for comparing, similarly do not carry out chemical plating processing (sample 9) to carrying out the pre-treatment polymer elements with the chemical plating liquid that contains alcohol, carry out the water system chemical plating liquid (will be above-mentioned containing the displaced chemical plating liquid of pure water in the chemical plating liquid of alcohol) that pretreated polymer elements utilization do not contain alcohol with treatment solution (a) (1,3 butylene glycol) and carry out chemical plating processing (sample 10).Carrying out aforesaid chemical plating when handling, the plating film growth time of individual sample (until the time that begins to separate out and until time of integral body lining) and the superficiality of plating film are being estimated.Superficiality is carried out following evaluation, promptly by visual inspection, zero defect ground forms on the whole under plated film and the no problem in appearance situation and is evaluated as zero, though formed plated film on the whole a part exist peel off or heave situation under be evaluated as △, exist under the situation that does not form the local of plated film or do not form plated film fully to be evaluated as *.

Then, for the sample that is formed with plated film, stacked use does not contain the plated film of the water system chemical plating liquid of alcohol on plated film, estimates the variation in the adaptation of plating film in following closing force and thermal cycling test.The results are shown in table 2.

Closing force

According to JIS H 8630 standards, (Tianjin, island makes society's system, AGS-100N) under the condition that 90 ° of angles, speed 25mm/ divide between the distance for 45mm, measures the power that plated film is peeled off from polymer elements to use tensile testing machine.

Thermal cycling test

Carry out the transformation temperature test between-40 ℃ and 100 ℃ of 50 round-robin.After the test,, be evaluated as zero under the no problem in appearance situation, be evaluated as △ under the situation that a generation part is peeled off or film is heaved on the plated film by the visual inspection plated film, be evaluated as under the whole situation of peeling off or heaving of plated film *.

Table 2

Shown in above-mentioned table as can be known, make up by pre-treatment that will utilize pure treatment solution and the chemical plating processing that utilizes the chemical plating liquid that contains alcohol, even for lower concentration be dispersed with the polymer elements of catalyst component, also can be under normal pressure, form plated film in the short period of time.In addition we know, when having high closing force by the plated film of this manufacture method manufacturing, the peeling off or heave lessly of plated film in thermal cycling test can form the plated film of adaptation excellence.Further as can be known, the pure treatment solution less by the content of water carries out pre-treatment, can form the plated film with higher closing force.

With respect to this, for the pretreated sample that does not utilize pure treatment solution or utilize the treatment solution only forms to carry out pretreated sample, need for a long time in order to separate out plated film, and can not form plated film on the whole by water.In addition we know, even utilize pure treatment solution to carry out pre-treatment, the sample for the chemical plating that does not utilize the chemical plating liquid that contains alcohol is handled does not form plated film.Therefore, for this sample, can not measure closing force or thermal cycling test.

Embodiment 2

Method for following formation plated film describes in the present embodiment, promptly make and catalyst component is dissolved in carbon dioxide pressurized pressure fluid contacts with flaky resin molded body by batch treatment, formation is dispersed with the sheet polymer parts of catalyst component, it is formed set shape by the preliminary shaping method, the sheet polymer portion of formed thereby is disposed in the mould, make sheet polymer parts and molten resin integrated by the embedded moulding method of film, on this incorporate polymer elements, handle forming plated film by chemical plating.Need to prove, in the present embodiment, use the nylon 6 film-making materials (エ of Mitsubishi Application ジニアリ Application グプラスチ Star Network ス society system as the flaky resin molding, ノバミ Star De 1020, thickness: 200 μ m), use identical hexafluoroacetylacetone palladium (II) complex compound with embodiment 1 as catalyst component.In addition, as by incorporate resin, using polyphthalamide resin (ソ Le ベイア De バ Application スト Port リマ one ズ (strain) society system, アモデ Le AS-1566) by the embedded shaping of film.

Dispersion steps

Fig. 2 is for being used to form the concise and to the point mode chart of the manufacturing installation of the sheet polymer parts that are dispersed with catalyst component in the present embodiment.As shown in Figure 2, thus this manufacturing installation has and is used to supply with carbon dioxide pressurized fluid supply unit 300, is used to make pressure fluid and flaky resin molding to contact to make catalyst component be scattered in the autoclaving portion 400 of flaky resin molding.

Fluid supply unit 300 has 2 Liquid carbon dioxide gas cylinders 301,302 and is used for Liquid carbon dioxide is forced into set pressure and supplies with carbon dioxide pressurized pump 303 and buffer container 304.In addition, the pipe arrangement that connects Liquid carbon dioxide gas cylinder 301,302 and pump 303 is provided with pressure warning unit 310, begins to be disposed with reducing valve 311, pressure warning unit 312 and self-acting valve 313 from upstream side on the pipe arrangement that connects buffer container 304 and autoclaving portion 400.

During with carbon dioxide pressurized supply autoclaving portion 400, open the manual valve 305,306 of Liquid carbon dioxide gas cylinder 301,302, after thereby the pipe arrangement that Liquid carbon dioxide is conditioned by temperature gasifies, and then boost by 303 pairs of carbonic acid gas of pump, make the pressure that is detected by pressure warning unit 310 reach set pressure.Thus, promptly the carbon dioxide pressurized of level pressure power is supplied in the buffer container 304.In addition, be supplied in the container 304 carbon dioxide pressurized by temperature regulation for after both reaching fixed temperature, reducing pressure to make by reducing valve 311 reaches set pressure, by opening self-acting valve 313 with the carbon dioxide pressurized autoclaving portion 400 that is supplied to.In the present embodiment, Liquid carbon dioxide from Liquid carbon dioxide gas cylinder 301,30 suction 4-6MPa, by being after 10 ℃ pipe arrangement gasifies, it to be boosted to pressure 15MPa by pump 303 by temperature regulation, and then to be supplied to temperature regulation be 50 ℃ buffer container 304.And make that by carbon dioxide pressurized decompressions of 311 pairs on reducing valve the pressure that detected by pressure warning unit 312 are 10MPa, after this with carbon dioxide pressurized supply autoclaving portion 400.

Autoclaving portion 400 has and is used to make flaky resin molding and the contacted high pressure vessel 401 of pressure fluid, shown in Fig. 2 and 3, hold coiling body 420 in high pressure vessel 401, this coiling body 420 is flaky resin molding L is wound onto across sieve diaphragm 421 on the cylinder 422 with a plurality of communicating poress and forms.This coiling body 420 inserts in the cylindric holding components 402 with a plurality of communicating poress that is arranged on central part in the high pressure vessel 401.As shown in Figure 2, the bottom of high pressure vessel 401 is provided with fluid supplying opening 403, be provided with fluid discharge outlet 404 on high pressure vessel 401 tops, above-mentioned fluid supplying opening 403 and fluid discharge outlet 404 are connected by circulation line 405, make pressure fluid at high pressure vessel 401 internal recycle.Between the connection section and fluid supplying opening 403 that are connected with fluid supply unit 300 of circulation line 405, be provided be used to make pressure fluid at the recycle pump 406 of circulation line 405 internal recycle, hold the dissolving tank 407 of catalyst component.In addition, connect the circulation line 405 of recycle pump 406 and dissolving tank 407, be connected in escape route 408, this escape route 408 is provided with pressure warning unit 409, self-acting valve 410 and back pressure valve 411.In view of the above, carbon dioxide pressurized from 300 supplies of fluid supply unit, by the recycle pump 406 carbon dioxide pressurized dissolving tanks 407 that are supplied to, dissolved at dissolving tank 407 inner catalyst compositions, the pressure fluid that contains catalyst component is supplied in the high pressure vessel 401.At this moment, back pressure valve 411 is set to set pressure, and is when the pressure of the pressure fluid in the circulation line 405 reduces, carbon dioxide pressurized additional from self-acting valve 313 quilts.On the other hand, the pressure of the pressure fluid in circulation line 405 is higher than under the situation of set pressure, and pressure fluid is discharged from by escape route 408.In view of the above, the pressure that reach in the circulation line 405 in the high pressure vessel 401 are maintained constant.In the present embodiment, the pressure of back pressure valve 411 and carbon dioxide pressurized pressure similarly are set to 10MPa, in high pressure vessel 401 and the pressure in the circulation line 405 maintain under the state of 10MPa and make circulation of pressurized fluid, handle, the feasible amount that is scattered in the catalyst component of flaky resin molding L is 10ppm.In addition, in the present embodiment, after processing, the temperature in the high pressure vessel 401 was kept 30 minutes down at 50 ℃, and then the temperature in the high pressure vessel 401 is warming up to 120 ℃, be incubated 30 minutes by not shown temperature regulation machine.Thus, thermal reduction is scattered in the metal complex of flaky resin molding L.Need to prove, the amount of catalyst component is calculated by following, be about to the flaky resin molding vacuumize initial stage sheet material weight before measuring dispersion steps under with dewatered state in 24 hours, and similarly measure dispersion steps after the weight of same sheet material, calculate by its variable quantity.

The embedded shaping project of film

Then, in the present embodiment, use the aforesaid sheet polymer parts that are dispersed with catalyst component, make the embedded shaping of molten resin and sheet integralization by the embedded moulding method of film.Particularly, at first, the sheet polymer parts are cut to both dimensionings, make polymer elements softening by the indirect heating source that utilizes infrared heater.After this, the forced air of stack polymer elements and blow gas pressure 1MPa makes the polymer elements driving fit on the preliminary shaping mould, thereby makes the mould shape transferred thereon in polymer elements on the preliminary shaping mould that will be formed by injection mold shown in Figure 4.Then, take off preformed polymer elements, form the polymer elements of box shape from the preliminary shaping mould.

Then, as shown in Figure 4, in the mold 510 that injection forming is used, disperse above-mentioned catalyst component, and insert preformed polymer elements M, carry out embedded shaping.Particularly, at first, shown in Fig. 4 (A), make the polymer elements M driving fit that forms the box shape, polymer elements M is fixed in moveable die 511 thereby then vacuumize by the groove 513 that vacuumizes usefulness in moveable die 511.After this, shown in Fig. 4 (B), moveable die 511 and fixed mould 512 being connected, is that the molten resins in the plasticity-cylinder 520 of arbitrary temp are packed in the mold 510 by the preceding of screw rod S and then injection with temperature regulation.Then, behind mold 510 mold closings, slough mold 510 then.Thus, obtain the polymer elements of embedded shaping.

Pre-treatment step

Then, the polymer elements of above-mentioned formation be impregnated in the pre-treatment of pure treatment solution.In the present embodiment, use the treatment solution (a) (1,3 butylene glycol) of embodiment 1, polymer elements is flooded under 100 ℃ therein carry out pre-treatment in 15 minutes as pure treatment solution.

The chemical plating step

Then, the chemical plating that above-mentioned pretreated polymer elements be impregnated in the chemical plating liquid that contains alcohol under normal pressure is handled.In the present embodiment similarly to Example 1, using the chemical plating liquid that contains 1,3 butylene glycol to carry out chemical plating under normal pressure handles.In addition, for relatively, similarly to Example 1, similarly do not use the chemical plating liquid that contains alcohol to carry out chemical plating processing (sample 12) for carrying out pretreated polymer elements.And then, will carry out water system chemical plating liquid that pretreated polymer elements utilization do not contain alcohol and carry out chemical plating and handle (sample 13).For above-mentioned each sample, similarly to Example 1, estimate the superficiality, closing force of growth time, the plated film of plated film, and by the adaptation of thermal cycling test test.It the results are shown in table 3.

Table 3

As above the table shown in as can be known, handle by pre-treatment that utilizes pure treatment solution and the chemical plating that utilizes the chemical plating liquid that contains alcohol, even for lower concentration be dispersed with the sheet polymer parts of catalyst component, also can be under normal pressure, the short period of time forms plated film on the whole.In addition we know, the plated film by this manufacture method manufacturing has high closing force.

With respect to this, even utilize the pretreated sample of pure treatment solution or utilize pure treatment solution to carry out the sample that pre-treatment still utilizes the chemical plating of the chemical plating liquid that contains alcohol to handle, still do not need for a long time even separate out plated film fully or separate out plated film, or can not form plated film on the whole until separating out.Therefore, for these samples, can not measure closing force.In addition, for the sample that does not form plated film fully, can not estimate thermal cycling test.

As mentioned above, manufacturing method according to the invention combines with utilizing the chemical plating processing of chemical plating liquid under normal pressure that contains alcohol in the pre-treatment under the normal pressure by utilizing pure treatment solution, can form the plated film of adaptation excellence.

In addition, describe for optimal way of the present invention, as follows.

(1) manufacture method that preferably has a polymer elements of plated film comprises:

Dispersion steps, the mode that wherein catalyst component is scattered in the resin molded body of shaping is, contact with resin molded body by making the catalyst component that contains the metal that becomes the plating catalyzer be dissolved in carbon dioxide pressurized pressure fluid, form the polymer elements that is dispersed with above-mentioned catalyst component;

Pre-treatment step impregnated in the above-mentioned polymer elements that is dispersed with catalyst component in the pure treatment solution under normal pressure; With

The chemical plating step, thus above-mentioned being impregnated under normal pressure in the chemical plating liquid that contains alcohol by the handled polymer elements of pure treatment solution formed plated film.

(2) in aforesaid way,, can use flaky resin molded body as resin molded body.

(3) in addition, the manufacture method that preferably has a polymer elements of plated film comprises:

Dispersion steps, in aforesaid way, utilize under the situation of the embedded moulding method of film, contact with the flaky resin molding by making the catalyst component that contains the metal that becomes the plating catalyzer be dissolved in carbon dioxide pressurized pressure fluid, form the sheet polymer parts that are dispersed with above-mentioned catalyst component;

Embedded forming step, in mould, injecting molten resin in above-mentioned mould makes above-mentioned sheet polymer parts and above-mentioned molten resin integrally formed with the above-mentioned sheet polymer component configuration that is dispersed with catalyst component;

Pre-treatment step is handled the polymer elements of above-mentioned embedded shaping under normal pressure by pure treatment solution; With

The chemical plating step impregnated in the chemical plating liquid that contains alcohol with the above-mentioned polymer elements of being handled by pure treatment solution under normal pressure, form plated film.

(4) manufacture method that preferably has a polymer elements of plated film comprises:

Dispersion steps, other modes that wherein make catalyst component be scattered in molten resin are, contact with molten resin by making the catalyst component that contains the metal that becomes the plating catalyzer be dissolved in carbon dioxide pressurized pressure fluid, the above-mentioned molten resin that is dispersed with catalyst component is passed through injection forming or extrusion molding, thereby form the above-mentioned polymer elements that is dispersed with catalyst component;

Pre-treatment step impregnated in pure treatment solution with the above-mentioned polymer elements that is dispersed with catalyst component under normal pressure; With

The chemical plating step impregnated in the chemical plating liquid that contains alcohol with above-mentioned by the handled polymer elements of pure treatment solution under normal pressure, thereby forms plated film.

(5) in addition, in aforesaid way, also can form the sheet polymer parts by extrusion molding.Promptly, can comprise in above-mentioned dispersion steps, contact with molten resin by making the catalyst component that contains the metal that becomes the plating catalyzer be dissolved in carbon dioxide pressurized pressure fluid, thereby the above-mentioned molten resin that is dispersed with catalyst component is formed the above-mentioned sheet polymer parts that are dispersed with catalyst component by extrusion molding.

(6) further, the manufacture method that preferably has the polymer elements of plated film comprises:

Dispersion steps, in above-mentioned other modes, for at the near surface greater concn ground of polymer elements dispersed catalyst composition, making the catalyst component that contains the metal that becomes the plating catalyzer be dissolved in carbon dioxide pressurized pressure fluid contacts with the 1st molten resin, above-mentioned the 1st molten resin that is dispersed with catalyst component is injected in the mould, and then in above-mentioned injection has the mould of the 1st molten resin that is dispersed with catalyst component, injection does not contain the 2nd molten resin of catalyst component, thereby forms the polymer elements that is dispersed with above-mentioned catalyst component;

(7) and, in above-mentioned other modes, it is organic solvent that pressure fluid preferably contains fluorine.

Claims

1. manufacture method with polymer elements of plated film comprises:

Dispersion steps utilizes the catalyst component that contains the metal that becomes the plating catalyzer to be dissolved in carbon dioxide pressurized pressure fluid, forms the polymer elements that is dispersed with described catalyst component;

Pre-treatment step impregnated in pure treatment solution with the polymer elements that is dispersed with described catalyst component under normal pressure; With

The chemical plating step impregnated in the chemical plating liquid that contains alcohol with described by the handled polymer elements of pure treatment solution under normal pressure, thereby forms plated film.

2. the manufacture method with polymer elements of plated film according to claim 1, wherein, described dispersion steps comprises: thus by being contacted with resin molded body, described pressure fluid forms the polymer elements that is dispersed with described catalyst component.

3. the manufacture method with polymer elements of plated film according to claim 2, wherein, described resin molded body is flaky resin molded body.

4. the manufacture method with polymer elements of plated film according to claim 3 wherein, after the described dispersion steps, before described pre-treatment step, further comprises:

Embedded forming step, in mould, injecting molten resin in described mould makes described sheet polymer parts and described molten resin integrally formed with the described sheet polymer component configuration that is dispersed with catalyst component.

5. the manufacture method with polymer elements of plated film according to claim 1, wherein, described dispersion steps comprises: described pressure fluid is contacted with molten resin, the molten resin that is dispersed with described catalyst component is passed through injection forming or extrusion molding, form the polymer elements that is dispersed with described catalyst component.

6. the manufacture method with polymer elements of plated film according to claim 1, wherein, described dispersion steps comprises: contact with the 1st molten resin by making described pressure fluid, the 1st molten resin that is dispersed with described catalyst component is injected in the mould, and then in described injection has the mould of the 1st molten resin that is dispersed with catalyst component, injection does not contain the 2nd molten resin of catalyst component, thereby forms the polymer elements that is dispersed with described catalyst component.

7. according to claim 5 or 6 described manufacture method with polymer elements of plated film, wherein, it is organic solvent that described pressure fluid also contains fluorine.